Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/06—Unsaturated polyesters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/24—Esters of carbonic or haloformic acids, e.g. allyl carbonate

Definitions

• the present invention relates to a liquid composition, polymerizable by the free-radical polymerization route, to yield organic glasses endowed with a high thermal stability.
• the invention relates also to the organic glasses which can be obtained from said composition.
• the present invention relates to a liquid composition polymerizable by free-­radical polymerization route and with a low shrinkage, to yield organic glasses endowed with high thermal stability, said composition being the product from the reaction, under transesterification conditions, of diallyl-carbonate (A) with a mixture of an either linear or branched aliphatic diol containing from 3 to 10 carbon atoms in its molecule (B), and an either linear or branched aliphatic, cycloaliphatic or heterocyclic polyol containing from 4 to 20 carbon atoms and from 3 to 6 hydroxy atoms in its molecule (C), or with a mixture of said (B) diol with a cycloaliphatic diol (C′), by operating with a molar ratio of A/(B+C) or of A/(B+C′) equal to, or higher than, 3/1, and with an amount of (C) in the (B+C) mixture equal to, or lower than, 70% by
• the values of the molar ratios of (A)/(B+C) and (A)/(B+C′) are kept comprised within a range of from 3/1 to 12/1, and the (C) and (C′) components are respectively present in an amount comprised within the range of from 20 to 60% and of from 20 to 80% by weight in the mixture (B+C) and (B+C′).
• the (B) diols useful for the purposes of the present invention are the either linear or branched aliphatic diols containing from 3 to 10 carbon atoms in their molecule.
• diols are diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butane-­diol, 1,6-hexane-diol, 1,3-propane-diol, neopentyl glycol, dipropylene glycol and 2,2,4-trimethyl-1,3-­pentanediol.
• diethylene glycol is preferred.
• the (C) polyols useful for the purposes of the present invention, are either linear or branched aliphatic, cycloaliphatic or heterocyclic diols, containing from 4 to 20 carbon atoms, and from 3 to 6 hydroxy groups in their molecule.
• polyols suitable for the intended purpose are: pentaerythritol, trimethylol­propane, di-pentaerythritol, di-trimethylol-propane and tris(hydroxyethyl)isocyanurate.
• pentaerythritol, trimethylolpropane and tris(hydroxyethyl)isocyanurate are preferred.
• the (C′) component useful for the intended purpose, is selected from cycloaliphatic, monocyclic or polycyclic diols, with 1,4-cyclohexane-di-methanol and 4,8 bis­(hydroxy-methyl)tricyclo[5.2.1.0. 2,6 ]decane.
• the composition according to the present invention is obtained by starting from diallyl-carbonate (A) and from the (B+C) or (B+C′) mixture by operating under transesterification conditions. More particularly, the process is carried out by placing the reactants into mutual contact, in the hereinabove stated proportions, and making them react at temperatures comprised within the range of from 80° to 160°C, and preferably of from 90° to 130°C in the presence of a catalyst of alkaline character, with the allyl alcohol which is formed as the reaction byproduct being continuously removed.
• Suitable catalysts for the intended purpose are hydroxides, carbonates and alkoxides of alkali metal, the organic bases and the basic ion-exchange resins.
• catalysts are sodium hydroxide, sodium carbonate, sodium methoxide.
• the catalyst is advantageously used in an amount equal to at least 1 ppm (part per million parts by weight), relatively to the sum of the weights of (B+C) or (B+C′) components, and preferably in amounts comprised within the range of from 0.01 to 0.3% by weight.
• the reaction is advantageously carried out under such a pressure that the system is made boil at the selected operating temperature, so as to favour the removal of allyl alcohol from the reaction mixture; e.g., pressure values comprised within the range of from 20 to 760 torr and preferably of from 50 to 400 torr are suitable for the intended purpose.
• reaction times are generally comprised within the range of from 0.5 to 20 hours, and typically are of the order of from 0.o to 2 hours.
• the reaction mixture After cooling, the reaction mixture is washed with water, in order to remove the small catalyst amounts, and, after de-mixing and separation of the aqueous phase, the unreacted diallyl carbonate is distilled off, by heating up to temperatures of the order of 120°C, under a decreasing pressure, with end pressure values of the order of 0.1-20 Torr, and preferably of 1-3 Torr, with the desired product being obtained as the residue.
• composition is finally submitted, if necessary, to filtration, after a preliminary treatment with activated charcoal.
• composition according to the present invention is liquid at room temperature, and has viscosity values comprised within the range of from 15 to 300 cst and density values of the order of 1.1 - 1.3 g/ml.
• the composition of the present invention is a complex mixture containing allyl-carbonates of the (B) component and of the (C) or (C′) component, in either monomer or oligomer form, as well as mixed oligomer allyl-carbonates of said (B) and (C) or (C′) components, with the relative amounts of said constituents of the composition mainly depending on the preselected ratios of the (A), (B) and (C) or (C′) reactants.
• This composition can be transformed into organic glasses, by means of free-radical polymerization, with the usual "casting" technique.
• one or more polymerization initiator(s) is(are) added, which are soluble in the same composition, and is(are) capable of generating free radicals at temperatures comprised within the range of from 30° to 120°C.
• Preferred examples of such initiators are di-cyclo-­hexyl-peroxy-dicarbonate, di-isopropyl-peroxy-dicarbon­ate, di-benzoyl-peroxide, di-sec.-butyl-peroxy-di­carbonate and sec.-butyl-cyclohexyl-peroxy-dicarbonate.
• the amount of initiator may generally vary within the range of from 1 to 6 parts by weight per each 100 parts by weight of the composition.
• the composition can additionally contain one or more conventional additive(s), such as stabilizers, lubricants, dyes, pigments, U.V.-absorbers, I.R.-­absorbers and the like, with the overall amount of such additives being anyway not higher than 1 part by weight per each 100 parts by weight of the same composition.
• additives such as stabilizers, lubricants, dyes, pigments, U.V.-absorbers, I.R.-­absorbers and the like, with the overall amount of such additives being anyway not higher than 1 part by weight per each 100 parts by weight of the same composition.
• composition of the present invention containing the initiator, and, possibly, one or more additive(s) selected from the above mentioned additives is transformed into the relevant organic glass by operating at temperatures comprised within the range of from 30° to 120°C, with polymerization times which can be generally comprised within the range of from 1 to 100 hours.
• the organic glasses obtained have a high thermal distorsion temperature (HDT higher than approximately 90°C, when determined by ASTM D-648), and a good set of optical and physical/mechanical characteristics.
• HDT high thermal distorsion temperature
• the so-obtained organic glasses are particularly useful in protecting shields (e.g., for welders), in sight windows (e.g., in blast furnaces), in windows in the transportation sector and in the civil building sector, in lenses for vehicle lights, in solar and photovoltaic collectors and panels, in substrates for optical disks and in panels for displays.
• shields e.g., for welders
• sight windows e.g., in blast furnaces
• windows in the transportation sector and in the civil building sector in lenses for vehicle lights, in solar and photovoltaic collectors and panels, in substrates for optical disks and in panels for displays.
• liquid polymerizable compositions are prepared by reacting, under transesterification conditions, diallyl-carbonate (A) and a mixture of the hydroxy-compounds.
• the (B) diol used in the examples is diethylene glycol (DEG).
• the (C) polyols used in the examples are: pentaerythritol (PE); tris-hydroxyethyl-isocyanurate (THEIC); and trimethylol-propane (TMP).
• the (C′) cycloaliphatic diol used in the examples is 1,4-cyclohexane-dimethanol.
• DCPD di-­cyclohexyl-peroxy-dicarbonate
• the catalyst-containing compositions are transformed by polymerization into flat sheets or neutral lenses, respectively of 3 mm and 2 mm of thickness, by means of the conventional casting technique.
• the liquid composition, containing the catalyst is cast into the hollow of a mould constituted by two glass elements, with a spacer gasket of plasticized polyvinyl-chloride or of ethylene-vinyl acetate copolymer (EVA).
• the liquid composition is then submitted to polymerization by means of a thermal treatment carried out for 72 hours inside a forced air circulation oven at 48°C.
• the moulds are opened and the polymerizates are recovered and are left standing at 110°C for a further 2 hours, in order to decompose any possible residues of initiator, and of relieving possible inner stresses.
• - Refractive index measured by Abbe refractometer (ASTM D-542); - Haze and transmittance at visible wave lengths (%): measured by using Gardner's Hazegard XL-211 (ASTM D-­1003); - Yellow index (YI), defined as: as determined by means of Gardner's XL-805 colorimeter (ASTM D-1925).
• the - Sutherland Abrasion Resistance is determined.
• the test consists in carrying out 25 abrasive cycles (50 passages), on the neutral lenses, of a pad of 2/0-type steel wool of 5.5 cm x 7.5 cm, loaded with a weight of 630 g.
• the abrasion degree produced is evaluated by means of the visual observation of the number, the length and the depth of the scratches, as compared to a corresponding reference sample based on diethylene glycol bis(allyl-carbonate) homopolymer.
• the abrasion resistance is expressed by means of a scoring on a scale of from 0 to 10, wherein score 10 is assigned to the scratch-free sample, or to a sample showing from one to three thin, not very deep scratches, and score 0 is assigned to the completely scratched sample (this is the case of diethylene glycol bis(allyl-carbonate) homo­polymer, assumed as the reference standard).
• Intermediate scores from 1 to 9 are assigned on the basis of the percentage of scratches shown by the tested sample, as compared to the reference standard. For example, if the sample shows a 60% of scratches relatively to the reference standard, its abrasion resistance value is 4; if it shows a 30% of scratches, its assigned score is 7, and so on.
• TMP Trimethylol-propane
• DEG Diethylene glycol
• DAC Diallyl-carbonate
• the reaction is carried out for 45 minutes at a temperature of 98-118°C, and under a pressure of 150 torr, with allyl alcohol being distilled off as it forms (total 230 g; purity of 99,0%).
• reaction mixture is washed with two portions of 500 ml each, of distilled water.
• diallyl-carbonate is distilled under 1 torr, with increasing temperature up to 120°C.
• the obtained product is decolorized by contact with 2% by weight of activated charcoal, for 4 hours at 80°C, and is then filtered.
• TBEIC Tris(hydroxyethyl)isocyanurate
• DEG Diethylene glycol
• DAC Diallyl-carbonate
• Solution at 30% by weight of sodium methoxide in methanol 0.15 ml.
• the reaction is carried out for 1.5 hours at a temperature of 116-119°C, and under a pressure of 150 torr, with allyl alcohol being distilled off as it forms (total 98 g; purity of 96%).
• reaction mixture is washed with two portions of 500 ml each, of distilled water.
• diallyl-carbonate is then distilled under 1 torr, with increasing temperature up to 120°C.
• the so obtained product is filtered over decalite.
• the reaction is carried out for 45 minutes at a temperature of 109-118°C, and under a pressure of 150 torr, with allyl alcohol being distilled off as it forms (total 218 g; purity of 90%).
• reaction mixture is washed with two portions of 500 ml each, of distilled water.
• diallyl-carbonate is then distilled under 1 torr, with increasing temperature up to 120°C.
• the so obtained product is decolorized with 2% by weight of activated charcoal for 4 hours at 80°C and is then filtered.
• the polymerizable compositions Nos. 1, 2, 3 and 4 are prepared by reacting diallyl-carbonate (DAC) with mixtures of pentaerythritol (PE) and diethylene glycol (DEG), at various molar ratios (R) of DAC to the sum of (PE+DEG), as shown in following Table 1.
• DAC diallyl-carbonate
• PE pentaerythritol
• DEG diethylene glycol
• compositions after the addition of di-cyclo­hexyl-peroxy-dicarbonate (DCPD); 5% by weight in the composition) are submitted to polymerization in the same way as previously set forth and on the hardened compositions, the characteristics reported in Table 2 are determined.
• DCPD di-cyclo­hexyl-peroxy-dicarbonate
• the polymerizable liquid compositions Nos. 5, 6 and 7 are prepared, by mixing triallyl-cyanurate (TAC) and diethylene glycol bis(allyl-carbonate) (BACGD), this latter being the product resulting from the transesterification between diallyl-carbonate and diethylene glycol in the mutual molar ratio of 12/1.
• TAC triallyl-cyanurate
• BACGD diethylene glycol bis(allyl-carbonate)
• DCPD di-cyclohexyl-peroxy-­dicarbonate
• the polymerizable liquid compositions Nos. 8, 9, and 10 are prepared by starting from diallyl-carbonate (DAC), tris(hydroxyethyl)isocyanurate (THEIC) and diethylene glycol (DEG), as shown in following Table 4.
• DAC diallyl-carbonate
• TOEIC tris(hydroxyethyl)isocyanurate
• DEG diethylene glycol
• DCPD di-cyclohexyl-peroxy-­dicarbonate
• the polymerizable compositions Nos. 11 and 12 are prepared by starting from diallyl-carbonate (DAC), trimethylol-propane (TMP) and diethylene glycol (DEG), as shown in following Table 6.
• DAC diallyl-carbonate
• TMP trimethylol-propane
• DEG diethylene glycol
• DCPD di-cyclohexyl-peroxy-­dicarbonate
• a liquid and polymerizable composition is prepared by starting from: - 1,4-Cyclohexane-dimethanol 138.7 g (0.96 mol) - Diethylene glycol 46.2 g (0.44 mol) - Diallyl-carbonate 795 g (5.6 mol) - Sodium methoxide, as a solution at 30% by weight of sodium methoxide in methanol 0.30 ml
• the reaction is carried out for 1 hour at a temperature of 114-121°C, and under a pressure of 150 torr, with allyl alcohol being distilled off as it forms (total 167 g; purity of 97%).
• reaction mixture is washed with two portions, of 500 ml each, of distilled water.
• diallyl-carbonate is then distilled off by operating under a pressure of 1 torr, with increasing temperature up to 120°C.
• the obtained product is decolorized with 2% by weight of activated charcoal, for 4 hours at 80°C, and is then filtered.
• the mixed cyclohexane-dimethanol and diethylene glycol bis(allyl-carbonate) dimer: R1 -CH2-CH2-O-CH2-CH2- is present in an amount of 10.3% by weight, and the relevant trimer is present in an amount of 5.2% by weight.
• the mixture contains furthermore an overall amount of 2.7% by weight of higher oligomers than the trimer.
• DCPD di-cyclohexyl-peroxy-­dicarbonate
• the reaction is carried out for 45 minutes at a temperature of 107-116°C, and under a pressure of 150 Torr, with allyl alcohol being distilled off as it forms (total 370 g).
• reaction mixture is washed with two portions of 1,000 ml each, of distilled water.
• diallyl-carbonate is distilled under 1 torr, with increasing temperature up to 120°C.
• the obtained product is decolorized by contact with 2% by weight of activated charcoal, for 4 hours at 80°C, and is then filtered.
• This product is a mixture of both monomer and oligomer cyclohexane-dimethanol bis(allyl-carbonate), neopentyl glycol bis(allyl-carbonate), and of mixed allyl-carbonates, having the following approximate composition: - Cyclohexane-dimethanol bis(allyl-carbonate): monomer 42% by weight; dimer 10% by weight; - Neopentyl glycol bis(allyl-carbonate): monomer 19% by weight; dimer 3% by weight; - Mixed bis(allyl-carbonate) 10% by weight; with the residual percentage being essentially constituted by the higher oligomers of the above species.

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• 1987
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